US5208195A - Process for the preparation of a catalyst for the hydration of olefins to give alcohols - Google Patents
Process for the preparation of a catalyst for the hydration of olefins to give alcohols Download PDFInfo
- Publication number
- US5208195A US5208195A US07/845,155 US84515592A US5208195A US 5208195 A US5208195 A US 5208195A US 84515592 A US84515592 A US 84515592A US 5208195 A US5208195 A US 5208195A
- Authority
- US
- United States
- Prior art keywords
- acid
- clay
- weight
- specific surface
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
Definitions
- the strength over a prolonged time-on-stream presents problems.
- the alumina-containing materials are distinguished by better mechanical strength, when they have an excessively high alumina content, they have the disadvantage that the alumina is dissolved away during the reaction by the action of the phosphoric acid.
- German Offenlegungsschrift 3,709,401 it was found that the good catalyst properties according to German Patent 2,908,491 and German Patent 2,929,919 with regard to long-term strength and good retention of the phosphoric acid are maintained in terms of the amount of alcohol produced per unit time and catalyst volume, can be considerably increased, this activity remaining virtually unchanged over a period of six months, if 20 to 40 per cent by weight, based on the total dry substance, of a fine-particled silica gel are added to the clay treated with acid in the first stage and having a high montmorillonite content, prior to molding for calcination, and the surface area and pore volume of the finished catalyst carrier is thus increased.
- the montmorillonite carrier alone in the leached state prior to impregnation with phosphoric acid has a specific surface area of only 150 to 160 m 2 /g and a pore volume of about 0.7 ml/g, it is not difficult to see that, as a result of the addition of, for example, 30% of silica gel (specific surface area about 350 m 2 /g), the specific surface area increases only linearly to 180-200 m 2 /g, whereas the pore volume (addition: silica gel 1.0 to 1.2 ml/g) increases disproportionately to 0.95-1.0 ml/g, which is critical for the increase in activity.
- the silica gel has a particle size distribution of between 30 and 60 ⁇ 10 -6 m, a pore volume of 0.9 to 1.7 ml/g, preferably 1 to 1.2 mg/g, and a specific surface area of 200 to 500 m 2 /g, preferably 380 to 400 m 2 /g.
- a milled natural raw clay which was chosen on the basis of a laboratory test so that, when treated for one hour with 20% strength hydrochloric acid at 82° C., not more than 5 g of K 2 O per kg of dry substance used are extracted, was heated for one hour with 20% strength hydrochloric acid at 82° C., the amount of acid being such that there were 8.4 mol of HCl per 1 kg of clay.
- the clay was washed acid-free and dried.
- a material having a residual aluminum content of 16 per cent by weight and a specific surface area of 300 m 2 /g was obtained.
- the catalyst spheres thus obtained were heated twice, for one hour in each case, with 20% strength hydrochloric acid at 100° to 110° C. and were washed acid-free with water. After drying at about 110° to 120 ° C., the alumina content in the spheres was determined as 1.4 per cent by weight and the titanium dioxide content of the spheres as 1.85% by weight. The specific surface area was 200 m 2 /g and the pore volume 0.94 ml/g. The spheres were then flooded with 40% strength by weight phosphoric acid, which acted for two hours, after which drying was carried out again at about 110° to 120° C. The spheres treated in this manner had an H 3 PO 4 content of 32 per cent by weight. The mean compressive strength was 80 Newton/sphere.
- a milled natural raw clay which was chosen on the basis of a laboratory test so that, when treated for one hour with 20% strength hydrochloric acid at 82° C., not more than 5 g of K 2 O per kg of dry substance used are extracted, was heated for one hour with 20% strength hydrochloric acid at 82° C., the amount of acid being such that there were 8.4 mol of HCl per one kg of clay, and was washed acid-free and dried.
- a material having a residual aluminum content of 16 per cent by and a specific surface area of 300 m 2 /g was obtained 30 parts of fine-particled silica gel from W. R.
- the specific surface area was 160 m 2 /g prior to impregnation with phosphoric acid, and the pore volume was 0.7 ml/g.
- an amount of only 135 g of ethanol was obtained per hour per liter of catalyst bed with this carrier in the synthesis of ethanol from ethylene and water.
Abstract
Description
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4107973 | 1991-03-13 | ||
DE4107973A DE4107973A1 (en) | 1991-03-13 | 1991-03-13 | METHOD FOR PRODUCING A CATALYST FOR HYDRATING OLEFINS TO ALCOHOLS |
Publications (1)
Publication Number | Publication Date |
---|---|
US5208195A true US5208195A (en) | 1993-05-04 |
Family
ID=6427092
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/845,155 Expired - Lifetime US5208195A (en) | 1991-03-13 | 1992-03-03 | Process for the preparation of a catalyst for the hydration of olefins to give alcohols |
Country Status (5)
Country | Link |
---|---|
US (1) | US5208195A (en) |
EP (1) | EP0503229B1 (en) |
JP (1) | JPH0639287A (en) |
CA (1) | CA2062658C (en) |
DE (2) | DE4107973A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5308812A (en) * | 1993-04-01 | 1994-05-03 | Bp America, Inc. | Treated pillared clays and alkylation process using same |
US5959164A (en) * | 1996-01-23 | 1999-09-28 | Degussa Huls Aktiengesellschaft | Use of catalysts based on catalyst supports containing silicon dioxide for catalytic reactions under hydrothermal conditions |
WO2001025149A2 (en) * | 1999-10-07 | 2001-04-12 | The Dow Chemical Company | Silica gel composition and method for making |
WO2002032841A1 (en) * | 2000-10-21 | 2002-04-25 | Bp Chemicals Limited | Process for the hydration of olefins |
WO2002100533A1 (en) * | 2001-06-08 | 2002-12-19 | Süd-Chemie AG | Method for the production of adsorption agent granules based on acid-activated laminar silicates and use thereof as catalyst |
US20040029718A1 (en) * | 1998-07-03 | 2004-02-12 | Degussa Ag | Dealuminized catalyst carrier, method of production, and method for hydrating C2 or C3 olefins with water |
US20040231307A1 (en) * | 2001-07-06 | 2004-11-25 | Wood Thomas E. | Inorganic fiber substrates for exhaust systems and methods of making same |
US20050202962A1 (en) * | 2000-10-21 | 2005-09-15 | Lansink Rotgerink Hermanus G.J. | Catalyst support |
EP2939995A1 (en) | 2014-04-30 | 2015-11-04 | Sasol Solvents Germany GmbH | Improved water management for the production of isopropyl alcohol by gas phase propylene hydration |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9214688D0 (en) † | 1992-07-10 | 1992-08-19 | Bp Chem Int Ltd | Olfin hydration catalysts |
DE4405876A1 (en) * | 1994-02-23 | 1995-10-05 | Sued Chemie Ag | Shaped catalyst or catalyst carrier bodies |
DE19601861A1 (en) * | 1996-01-19 | 1997-07-24 | Sued Chemie Ag | High-porosity catalyst support for olefin-hydration catalyst etc. |
DE19607494A1 (en) * | 1996-02-28 | 1997-09-04 | Degussa | Use of catalysts based on silicon dioxide-containing catalyst supports for catalytic reactions under hydrothermal conditions |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2713560A (en) * | 1951-03-26 | 1955-07-19 | Jacque C Morrell | Catalyst and methods of making same |
US2862875A (en) * | 1953-04-30 | 1958-12-02 | Jacque C Morrell | Conversion of hydrocarbons with the use of a kaolin composite catalyst |
US3311568A (en) * | 1965-02-01 | 1967-03-28 | Nii Sint Spirtov I Orch Produk | Method for production of catalyst for hydration of olefins to alcohols |
GB1371905A (en) * | 1971-07-27 | 1974-10-30 | Bp Chem Int Ltd | Olefin hydration catalyst and use thereof in alcohol production |
US4808559A (en) * | 1987-03-21 | 1989-02-28 | Huls Aktiengesellschaft | Method of manufacturing a catalyst for hydration of olefins to alcohols |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1075895A (en) * | 1964-06-21 | 1967-07-12 | Nii Sint Spirtov I Orch Produk | Improvements relating to catalysis |
-
1991
- 1991-03-13 DE DE4107973A patent/DE4107973A1/en not_active Withdrawn
-
1992
- 1992-01-15 DE DE59202579T patent/DE59202579D1/en not_active Expired - Fee Related
- 1992-01-15 EP EP92100551A patent/EP0503229B1/en not_active Expired - Lifetime
- 1992-03-03 US US07/845,155 patent/US5208195A/en not_active Expired - Lifetime
- 1992-03-11 CA CA002062658A patent/CA2062658C/en not_active Expired - Fee Related
- 1992-03-12 JP JP4053774A patent/JPH0639287A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2713560A (en) * | 1951-03-26 | 1955-07-19 | Jacque C Morrell | Catalyst and methods of making same |
US2862875A (en) * | 1953-04-30 | 1958-12-02 | Jacque C Morrell | Conversion of hydrocarbons with the use of a kaolin composite catalyst |
US3311568A (en) * | 1965-02-01 | 1967-03-28 | Nii Sint Spirtov I Orch Produk | Method for production of catalyst for hydration of olefins to alcohols |
GB1371905A (en) * | 1971-07-27 | 1974-10-30 | Bp Chem Int Ltd | Olefin hydration catalyst and use thereof in alcohol production |
US4808559A (en) * | 1987-03-21 | 1989-02-28 | Huls Aktiengesellschaft | Method of manufacturing a catalyst for hydration of olefins to alcohols |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5308812A (en) * | 1993-04-01 | 1994-05-03 | Bp America, Inc. | Treated pillared clays and alkylation process using same |
US5959164A (en) * | 1996-01-23 | 1999-09-28 | Degussa Huls Aktiengesellschaft | Use of catalysts based on catalyst supports containing silicon dioxide for catalytic reactions under hydrothermal conditions |
US6881700B2 (en) | 1998-07-03 | 2005-04-19 | Sasol Germany Gmbh | Dealuminized catalyst carrier, method of production, and method for hydrating C2 or C3 olefins with water |
US6881699B1 (en) * | 1998-07-03 | 2005-04-19 | Sasol Germany Gmbh | Method for producing a dealuminized catalyst support |
US20040029718A1 (en) * | 1998-07-03 | 2004-02-12 | Degussa Ag | Dealuminized catalyst carrier, method of production, and method for hydrating C2 or C3 olefins with water |
WO2001025149A2 (en) * | 1999-10-07 | 2001-04-12 | The Dow Chemical Company | Silica gel composition and method for making |
WO2001025149A3 (en) * | 1999-10-07 | 2002-03-14 | Dow Chemical Co | Silica gel composition and method for making |
US20050202962A1 (en) * | 2000-10-21 | 2005-09-15 | Lansink Rotgerink Hermanus G.J. | Catalyst support |
US20040044257A1 (en) * | 2000-10-21 | 2004-03-04 | Cockman Russell William | Process for the hydration of olefins |
WO2002032841A1 (en) * | 2000-10-21 | 2002-04-25 | Bp Chemicals Limited | Process for the hydration of olefins |
US6953867B2 (en) | 2000-10-21 | 2005-10-11 | Innovene Europe Limited | Process for the hydration of olefins |
US6989345B2 (en) | 2000-10-21 | 2006-01-24 | Degussa Ag | Catalyst support |
US7148179B2 (en) | 2000-10-21 | 2006-12-12 | Degussa Ag | Catalyst support |
US20040186017A1 (en) * | 2001-06-08 | 2004-09-23 | Uwe Flessner | Method for the production of adsorption agent granules based on acid-activated laminar silicates and use thereof as catalyst |
WO2002100533A1 (en) * | 2001-06-08 | 2002-12-19 | Süd-Chemie AG | Method for the production of adsorption agent granules based on acid-activated laminar silicates and use thereof as catalyst |
US7053023B2 (en) | 2001-06-08 | 2006-05-30 | Sud-Chemie Ag | Method for the production of adsorption agent granules based on acid-activated layer silicates |
US20040231307A1 (en) * | 2001-07-06 | 2004-11-25 | Wood Thomas E. | Inorganic fiber substrates for exhaust systems and methods of making same |
US7404840B2 (en) * | 2001-07-06 | 2008-07-29 | 3M Innovative Properties Company | Chemically stabilized β-cristobalite and ceramic bodies comprising same |
EP2939995A1 (en) | 2014-04-30 | 2015-11-04 | Sasol Solvents Germany GmbH | Improved water management for the production of isopropyl alcohol by gas phase propylene hydration |
Also Published As
Publication number | Publication date |
---|---|
JPH0639287A (en) | 1994-02-15 |
CA2062658C (en) | 2001-11-20 |
DE59202579D1 (en) | 1995-07-27 |
DE4107973A1 (en) | 1992-09-17 |
CA2062658A1 (en) | 1992-09-14 |
EP0503229A1 (en) | 1992-09-16 |
EP0503229B1 (en) | 1995-06-21 |
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Legal Events
Date | Code | Title | Description |
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Owner name: HUELS AKTIENGESELLSCHAFT, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SCHLUETER, DIETRICH;BAUMEISTER, FRANZ-JOSEF;SCHUBERT, KLAUS-PETER;REEL/FRAME:006483/0147 Effective date: 19930113 |
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Owner name: DEGUSSA-HUELS AKTIENGESELLSCHAFT, GERMANY Free format text: MERGER;ASSIGNOR:HUELS AKTIENGESELLSCHAFT;REEL/FRAME:011837/0001 Effective date: 19990201 |
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